Light-Induced Remodeling of Physically Crosslinked Hydrogels Using Near-IR Wavelengths.

Poly([6-bromo-7-hydroxycoumarin-4-yl]methyl methacrylate)-based triblock copolymers were synthesized by first preparing PMAA-PEG-PMAA triblocks using ATRP. 6-Bromo-4-chloromethyl-7-hydroxycoumarin was conjugated to PMAA-PEG-PMAA using 1,8-diazabicycloundec-7-ene (DBU). Rheological measurements were conducted using a HR-2 rheometer with a UV illumination accessory (TA Instruments). Single-photon uncaging was performed as previously described.20 Two-photon uncaging was performed using a LSM (Zeiss) equipped with a Ti: Sapphire laser (Coherent). All values reported as mean ± std. dev. unless otherwise stated. See Supporting Information for experimental details.

[1]  L. Hazleton,et al.  Toxicity of coumarin. , 1956, The Journal of pharmacology and experimental therapeutics.

[2]  Kristi S Anseth,et al.  Controlled two-photon photodegradation of PEG hydrogels to study and manipulate subcellular interactions on soft materials. , 2010, Soft matter.

[3]  D. Häder,et al.  UV-induced DNA damage and repair: a review , 2002, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[4]  T. Furuta.  Designing Caged Compounds for Spatiotemporal Control of Cellular Chemistry , 2012 .

[5]  B. Lake,et al.  Coumarin metabolism, toxicity and carcinogenicity: relevance for human risk assessment. , 1999, Food and chemical toxicology : an international journal published for the British Industrial Biological Research Association.

[6]  Ying Luo,et al.  A photolabile hydrogel for guided three-dimensional cell growth and migration , 2004, Nature materials.

[7]  Junsang Doh,et al.  Photogenerated polyelectrolyte bilayers from an aqueous-processible photoresist for multicomponent protein patterning. , 2004, Journal of the American Chemical Society.

[8]  Adah Almutairi,et al.  Low power, biologically benign NIR light triggers polymer disassembly. , 2011, Macromolecules.

[9]  Yu-Li Wang,et al.  A photo-modulatable material for probing cellular responses to substrate rigidity. , 2009, Soft matter.

[10]  Yan Liu,et al.  Effective crosslinking densities and elastic moduli of some physically crosslinked hydrogels , 1995 .

[11]  Adah Almutairi,et al.  A Single UV or Near IR Triggering Event Leads to Polymer Degradation into Small Molecules. , 2012, ACS macro letters.

[12]  W. Denk,et al.  Deep tissue two-photon microscopy , 2005, Nature Methods.

[13]  J. Allard,et al.  A new two-photon-sensitive block copolymer nanocarrier. , 2009, Angewandte Chemie.

[14]  K. A. Davis,et al.  Block copolymers of poly(styrene) and poly(acrylic acid) of various molar masses, topologies, and compositions prepared via controlled/ living radical polymerization. Application as stabilizers in emulsion polymerization , 2001 .

[15]  Julian H. George,et al.  Exploring and Engineering the Cell Surface Interface , 2005, Science.

[16]  Jean-François Gohy,et al.  Synthesis and self-assembly of diblock copolymers bearing 2-nitrobenzyl photocleavable side groups† , 2012 .

[17]  Kristi S. Anseth,et al.  Photodegradable Hydrogels for Dynamic Tuning of Physical and Chemical Properties , 2009, Science.

[18]  Pj Piet Lemstra,et al.  “Controlled” Synthesis and Characterization of High Molecular Weight Methyl Methacrylate/tert-Butyl Methacrylate Diblock Copolymers via ATRP , 2003 .

[19]  E M Callaway,et al.  Brominated 7-hydroxycoumarin-4-ylmethyls: photolabile protecting groups with biologically useful cross-sections for two photon photolysis. , 1999, Proceedings of the National Academy of Sciences of the United States of America.

[20]  Kristi S. Anseth,et al.  Mixed Mode Thiol−Acrylate Photopolymerizations for the Synthesis of PEG−Peptide Hydrogels , 2008 .

[21]  John-Christopher Boyer,et al.  Near-infrared light-triggered dissociation of block copolymer micelles using upconverting nanoparticles. , 2011, Journal of the American Chemical Society.

[22]  John-Christopher Boyer,et al.  Near infrared light triggered release of biomacromolecules from hydrogels loaded with upconversion nanoparticles. , 2012, Journal of the American Chemical Society.

[23]  Chulhee Kim,et al.  Photoinduced release of guest molecules by supramolecular transformation of self-assembled aggregates derived from dendrons. , 2008, Angewandte Chemie.

[24]  Adah Almutairi,et al.  UV and near-IR triggered release from polymeric nanoparticles. , 2010, Journal of the American Chemical Society.

[25]  Kristi S Anseth,et al.  In situ elasticity modulation with dynamic substrates to direct cell phenotype. , 2010, Biomaterials.

[26]  M. Shoichet,et al.  Two-photon micropatterning of amines within an agarose hydrogel , 2008 .

[27]  Yue Zhao,et al.  Toward Photocontrolled Release Using Light-Dissociable Block Copolymer Micelles , 2006 .

[28]  A. Kasko,et al.  Photodegradable macromers and hydrogels for live cell encapsulation and release. , 2012, Journal of the American Chemical Society.

[29]  A. Khademhosseini,et al.  Hydrogels in Regenerative Medicine , 2009, Advanced materials.

[30]  Andrea M. Kasko,et al.  Photodegradable Hydrogels to Generate Positive and Negative Features over Multiple Length Scales , 2010 .

[31]  M. C. Stuart,et al.  Thin polymer films as sacrificial layers for easier cleaning , 2010 .

[32]  Panagiotis Argitis,et al.  Photodegradable polymers for biotechnological applications. , 2012, Macromolecular rapid communications.

[33]  Jean-François Gohy,et al.  Photo-responsive block copolymer micelles: design and behavior. , 2013, Chemical Society reviews.

[34]  C. Bettinger,et al.  Light-induced disintegration of robust physically cross-linked polymer networks. , 2013, Macromolecular rapid communications.

[35]  T. Nishikubo,et al.  Synthesis of polymers in aqueous solutions: Esterification reaction of poly(methacrylic acid) with alkyl halides using DBU in aqueous solutions , 1996 .

[36]  W. Meier,et al.  Synthesis of Photocleavable Amphiphilic Block Copolymers: Toward the Design of Photosensitive Nanocarriers , 2010 .